Theoretical Photoelectron Spectroscopy of Metal–Metal Quintuple Bonds: Relativity-Driven Reordering of Frontier Orbitals

IF 3.3 Q2 CHEMISTRY, MULTIDISCIPLINARY ACS Organic & Inorganic Au Pub Date : 2024-03-01 DOI:10.1021/acsorginorgau.4c00002
Abhik Ghosh*,  and , Jeanet Conradie*, 
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Abstract

A recent reinvestigation of the gas-phase photoelectron spectra of Group 6 metal–metal quadruple-bonded complexes with scalar-relativistic DFT calculations showed that common exchange-correlation functionals reproduce the lowest ionization potentials in a semiquantitative manner. The finding encouraged us to undertake a DFT study of metal–metal quintuple bonds in a set of bisamidinato complexes with the formula MI2[HC(NR)2]2 (M = Cr, Mo, W; R = H, Ph, 2,6-iPr2C6H3) and idealized D2h symmetry. Scalar-relativistic OLYP/STO-TZ2P calculations indicated significant shifts in valence orbital energies among the three metals, which translate to lower first ionization potentials, higher electron affinities, and lower HOMO–LUMO gaps for the W complexes relative to their Cr and Mo counterparts. These differences are largely attributable to substantially larger relativistic effects in the case of tungsten relative to those of its lighter congeners.

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金属-金属五键的理论光电子能谱学:相对论驱动的前沿轨道重排
最近通过标量相对论 DFT 计算对第 6 族金属-金属四键配合物的气相光电子能谱进行了重新研究,结果表明常见的交换相关函数以半定量的方式再现了最低电离电位。这一发现鼓励我们对一组双脒基配合物中的金属-金属五键进行 DFT 研究,这些配合物的化学式为 MI2[HC(NR)2]2(M = Cr、Mo、W;R = H、Ph、2,6-iPr2C6H3),对称性为理想化的 D2h。标量相对论 OLYP/STO-TZ2P 计算表明,这三种金属的价轨道能量发生了显著变化,因此相对于 Cr 和 Mo 复合物而言,W 复合物的第一电离电位更低、电子亲和力更高、HOMO-LUMO 间隙更小。这些差异在很大程度上归因于钨相对于其较轻同系物的更大相对论效应。
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ACS Organic & Inorganic Au
ACS Organic & Inorganic Au 有机化学、无机化学-
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4.10
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期刊介绍: ACS Organic & Inorganic Au is an open access journal that publishes original experimental and theoretical/computational studies on organic organometallic inorganic crystal growth and engineering and organic process chemistry. Short letters comprehensive articles reviews and perspectives are welcome on topics that include:Organic chemistry Organometallic chemistry Inorganic Chemistry and Organic Process Chemistry.
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